Polymeric resins derived from 1-oxa-3-aza tetraline group-containing compounds and cycloaliphatic epoxides

ABSTRACT

A composition comprising a polymeric resin derived from (A) at least one compound containing an average of more than one 1-oxa-3-aza-tetraline group per molecule with (B) at least one cycloaliphatic epoxide containing at least two epoxide groups, at least one of said epoxide groups being part of said ring, the mole ratio of (B) to (A) being in the range of about 0.2 to about 2.

TECHNICAL FIELD

This invention relates to polymeric resins derived from 1-oxa-3-azatetraline group-containing compounds and cycloaliphatic epoxides. Moreparticularly, this invention relates .Iadd.to .Iaddend.polymeric resinsderived from compounds containing an average of more than 1-oxa-3-azatetraline group, and cycloaliphatic epoxides containing at least onealiphatic ring and an average of at least two epoxide groups, at leastone of said epoxide groups being part of said ring.

BACKGROUND OF THE INVENTION

Compounds containing 1-oxa-3-aza-tetraline groups, and theirprepolymers, are known, for example, from Swiss Pat. Nos. 574,978,579,113 and 606,169. They can be obtained, for example, from phenols byreaction with formaldehyde and an amine, according to the formula:##STR1## wherein R is, for example, hydrogen, halogen, alkyl or alkoxy,and R' is an aliphatic or aromatic group. In contrary to other knowncondensation reactions of phenols, amines and formaldehyde, in thereaction outlined above phenolic OH-groups are consumed. It is therebypossible, according to the formula (a) hereinabove, to determine theamount of the synthesized 1-oxa-3-aza tetraline group from the analyticdetermination of the said OH-groups in the rection mixture.

It is also known from the above-mentioned patents that these compoundscontaining 1-oxa-3-aza-tetraline groups can be cured with epoxideresins, including cycloaliphatic epoxide resins. The products obtainedup to now have been useful for various applications, but their stabilityis limited. The Martens heat stability of the hardest resins obtained upto now is only between about 120° C. and 135° C., with peak values fromabout 160° C. to 170° C.

For many applications, higher heat stabilities are necessary. Forexample, electric insulating materials of high heat stability are aconstant requirement of the electric industry. Plastics reinforced withglass, quartz, carbon fibers and the like would probably be consideredfor many new areas of application if the heat resistance of thepolymeric resin could be increased.

SUMMARY OF THE INVENTION

The present invention contemplates the provision of polymeric resinscharacterized by particularly outstanding heat stabilities incombination with good mechanical properties. Broadly stated, the presentinvention provides for a composition comprising a polymeric resinderived from (A) at least one compound containing an average of morethan one 1-oxa-3-aza tetraline group per molecule with (B) at least onecycloaliphatic epoxide containing at least one aliphatic ring and anaverage of at least two epoxide groups, at least one of said epoxidegroups being part of said ring, the mole ratio of (B) to (A) being inthe range of about 0.2 to about 2.

DESCRIPTION OF THE PREFERRED EMBODIMENT

The polymeric resins provided in accordance with the present inventionare derived from (A) compounds containing an average of more thanone-1-oxa-3-aza-tetraline group per molecule and/or .[.per.]. .Iadd.the.Iaddend.pre-polymer of said compound and (B) cycloaliphatic epoxidescontaining at least one aliphatic ring and an average of at least twoepoxide groups per molecule, at least one of said epoxide groups beingpart of said aliphatic ring and the remaining epoxide groups eitherbeing part of said ring or being directly attached to said ring.

Throughout this specification and in the appended claims, theterminology "part of a ring" with respect to the position of an epoxidegroup on an aliphatic ring refers to the following structure ##STR2##The terminology "directly attached to a ring" refers to the followingstructure ##STR3##

Compounds with more than one 1-oxa-3-aza-tetraline group in the moleculecan be obtained from polyvalent phenols and/or amines, according to oneof the following reaction schemes (b) or (c), or can be obtained byother methods known in the art.

In .[.contrary.]. .Iadd.contrast .Iaddend.to other known condensationreactions of phenols, amines and formaldehyde, in the reaction outlinedabove phenolic OH-groups are consumed. It is thereby possible, accordingto the formula (a) hereinabove, to determine the amount of thesynthesized 1-oxa-3-aza tetraline groups from the analytic determinationof the said OH-groups in the reaction mixture. ##STR4## is the nth partof a phenol with n phenol OH groups;

A is the group resulting from ##STR5## after splitting off of OH and Hin ortho position;

R' is an aliphatic or, preferably, an aromatic group; and

n is a number greater than 1, preferably less than 6, more preferablyfrom about 1.5 to about 3. ##STR6## wherein:

B is the mth part of a m-valent aliphatic or, preferably, aromaticgroup, which may also contain hetero atoms, especially oxygen, or may besubstituted by R;

R is hydrogen, halogen, alkyl or alkoxy with 1 to about 6 carbon atoms,preferably in metα- or para-position of the phenol; and

m is a number greater than 1, preferably less than about 6, morepreferably from about 1.5 to about 3.

The phenol nuclei may also be part of a condensed ring system.

Values of n or m that are not whole numbers mean that mixtures ofdifferent functional phenols or amines with the average value n or m areprovided.

Suitable for use as 1-oxa-3-aza-tetraline group containing compounds are.Iadd.also .Iaddend.the reaction products which are prepared, forexample, in accordance with the teachings of Swiss Pat. No. 606,169(which is incorporated herein by reference), from phenols, amines andformaldehyde in non-stoichiometric proportions. Mole ratios of thereactants that provide an average of more than one 1-oxa-3-aza tetralinegroup per molecule must be used.

Prepolymers of 1-oxa-3-aza-tetraline group containing compounds are alsouseful in accordance with the invention. Since some of the1-oxa-3-aza-tetraline groups may react during polymerization, theseprepolymers may contain a fewer number of said 1-oxa-3-aza-tetralinegroups than provided by the monomers used to form such prepolymers. Itis essential, however, that the .[.resulting prepolymers.]..Iadd.intermediate monomer reaction products .Iaddend.contain more thanone 1-oxa-3-aza-tetraline group per molecule. This can be calculated bya skilled artisan from the functionality and the ratios of startingmaterials.

A 1-oxa-3-aza-tetraline composition according to the invention or theprepolymers thereof are obtained, for example, if per mole ofmultifunctional phenol or amine more than two moles of formaldehyde andmore than one mole of monofunctional amine and phenol, respectively, arebrought into reaction, whereby the mole proportions are within the limitdefined by the disclosure of Swiss Pat. No. 606,169.

The reactants for forming the 1oxa-3-aza-tetraline group containingcompounds of the invention are phenols or phenol derivatives, amines andformaldehyde. Examples of phenols that can be used include monovalentphenols, such as phenol and m- and p-cresol, m- and p-ethyl-phenol, m-and p-isopropylphenol, m- and p-methoxy-phenol, m- and p-ethoxy-phenol,m-and p-isopropyloxy-phenol, m- and p-chloro-phenol and B-naphthol.Meta-substituted phenols are preferred, since they do not include anyblocked reactive positions. Ortho-substituted phenols are lessappropriate. Bivalent phenols that are useful include4,4'-dihydroxy-diphenylmethane, 3,3'-dihydroxydiphenylmethane,2,2-bis-(4-hydroxyphenyl)-propane, 4,4'-dihydroxy-stilbene,hydroquinone, pyrocatechin and resorcin. Novolak resins.Iadd.,eventually .Iaddend.mixed with a phenol.Iadd., .Iaddend.can also beused.

Examples of amines that are useful include aniline, o-, m- andp-phenylene diamine, benzidine, 4,4'-diaminodiphenyl methane and2,2-bis-(aminophenyl)propane.

The epoxides are preferably bivalent or polyvalent cycloaliphaticepoxides containing at least one epoxide group in a ring, and theremaining epoxide groups also in a ring or directly attached to a ring.Preferred epoxides are epoxide resins represented by the formula

    X--Y

wherein:

X is a 3,4-epoxycyclohexyl group or a mono- or dimethyl substituted3,4-epoxycyclohexyl group; and

Y is a group of the formula ##STR7## wherein n is a number in the rangeof from zero to 2, or a group of the formula ##STR8## or a group of theformulae

    --COO--CH.sub.2 --X

or

    --CH.sub.2 --Z--CH.sub.2 --X

wherein:

X is as defined above, and Z is .[.derived from.]. .Iadd.the acidradical of .Iaddend.an aliphatic, cycloaliphatic or aromaticdicarboxylic acid, such as, for example, adipic acid, terephthalic acidor 4,5-epoxy-hexahydrophthalic acid.

Particularly preferred epoxides are epoxide resins having equivalentweights in the range of from about 70 to about 250, preferably fromabout 120 to about 200.

Examples of epoxides that can be used include2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, 1 to4 times methylated 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, 4-(1,2-epoxyethyl)-1,2-epoxycyclohexane,1,2,8,9-diepoxy-p-.[.methane.]. .Iadd.menthane.Iaddend.,2,2-bis(3,4-epoxycyclohexyl)propane, bis-(2,3-epoxycyclopentyl) ether,1,2,5,6-diepoxy-4,7-hexahydromethanoindane,bis-(3,4-epoxy-cyclohexylmethyl) adipate,bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate,bis-(3,4-epoxy-cyclohexylmethyl)terephthalate,bis-(3,4-epoxy-6-methyl-cyclohexylmethyl)-terephthalate,3,4-epoxy-cyclohexanecarboxylic acid-(3,4-epoxy-cyclohexylmethyl) ester,3,4-epoxy-6-methylcyclohexanecarboxylicacid-(3,4-epoxy-6-methylcyclohexylmethyl)ester,1,2-bis-(5(1,2-epoxy)-4,7-hexahydromethanoindane oxy)-ethane.[.1,1,1-tris((5-(1,2-epoxy)-4,7-hexahydromethynoindaneoxy)-methyl)-propane.]..Iadd.1,1,1-tris((5-(1,2-epoxy-4,7-hexahydromethanoindaneoxy)-methyl)-propane .Iaddend.and 4,5-epoxyhexahydrophthalicacid-bis-(3,4-epoxycyclohexylmethyl)ester. Particularly preferredepoxide resins include 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, 1 to 4 times methylated 2-(3,4-epoxy)cyclohexyl-5,5-spiro (3,4-epoxy)cyclohexane-m-dioxane,bis(3,4-epoxy-cyclohexylmethyl)adipate,bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate,3,4-epoxy-cyclohexane-carboxylic acid-(3,4-epoxy-cyclohexylmethyl) esterand 3,4-epoxy-6-methylcyclohexane carboxylicacid-(3,4-epoxy-6-methylcyclohexylmethyl) ester.

The mole ratio of .[.epoxides.]. .Iadd.epoxide groups .Iaddend.to1-oxa-3-aza-tetraline .[.group containing compounds.]. .Iadd.groups.Iaddend.that are useful in accordance with the invention are preferablyin the range of from about 0.2 to about 2, more preferably from about0.8 to about 1.5

For purposes of calculating equivalent ratios, the number of equivalentsof a 1-oxa-3-aza-tetraline group containing compound is based on theamount of primary amine brought into reaction; independently of whetherit actually forms part of a 1-oxa-3-aza-tetraline group. It is assumedthat for each mole of formaldehyde that is reacted, one mole of waterwill be split off. Thus, for example, in Example 6 below, thetheoretical equivalent weight of the 1oxa-3-aza-tetraline groupcontaining compound is based on the following calculation

    ______________________________________                                        1 gram equivalent                                                                         Novolak (equiv. weight = 100) =                                                                    100 g                                        +0.8 mole   .[.analine.]..Iadd.aniline =                                                                       74.4 g                                       +1.5 mole   formaldehyde =       45 g                                         -1.5 mole   water =              -27 g                                                    =                    192.4 g                                      ______________________________________                                    

The N-equivalent weight is equal to 192.4 divided by 0.8 which equals240.5.

If, in the production of the 1-oxa-3-aza-tetraline group containingcompounds, no other nitrogen compounds other than the primary amines areadded, the equivalent weight may also be calculated from the nitrogencontent using known techniques. Compounds with more than one1-oxa-3-aza-tetraline group per molecule have N-equivalent weights thatare less than the average molecular weight.

The reaction between the 1-oxa-3-aza-tetraline group containing compoundand epoxide, which is in effect a curing reaction, is preferablyconducted at a temperature in the range of about 50° C. to about 300+C., more preferably about 100° C. to about 250° C., more preferablyabout 140° C. to about 230° C.

For various applications, it is advantageous to initially carry out thecuring in at least two steps to produce as an intermediate product asolid or highly viscous, but still soluble or meltable, prepolymer.Alternatively, the prepolymer can be formed during the production of the1-oxa-3-aza-tetraline group containing compound .[.prior toreaction.]..Iadd., or it can be formed prior to, during or after thereaction .Iaddend.with the epoxide. The final curing step is thenpreferably carried out at a temperature in the range of about 140° C. toabout 230° C.

The final curing step can be improved by addition of a catalyst toaccelerate the reaction. In particular, the curing time can be shortenedin this way. Examples of catalysts that can be used include, forexample, acids, Friedel-Crafts catalysts, amines, phosphines orquaternizing agents for tertiary amines, and especially alkyl, aralkyland aryl halides or sulfates, such as, for example, benzyl chloride,chlorobenzol, iodobenzol, iodoform, bromoform, methyl iodide or methylsulfate.

Prior to or during the curing reaction to produce the polymeric resinsof the invention, additives such as fillers, colorants, reinforcingfibers, plasticizers and the like can be added to the reaction mixture.These additives can be provied at levels of up to, for example, about50% by weight of reaction mixture.[., preferably from about 10% to about20% by weight of the mixture.].. The polymeric resins of the inventioncan also be combined with other plastics, resins or polymerizablemonomers or prepolymers such as, for example, aldehyde condensationresins (e.g., phenol formaldehyde resins.Iadd.) .Iaddend.and otherepoxide resins.[.) prior to or during curing.]. .Iadd.as well as curingagents of these resins.Iaddend.. The amount of the above mentionedadditives which may be mixed with resin according to the invention orwhich are soluble therein should not exceed 50% of the mixture andpreferably should be in the region of 10 to 20%.

The polymeric resins of the present invention can be used for manypurposes such as, for example, casting, laminating, impregnating,coating, gluing, painting, binding or insulating, or in embedding,pressing, injection molding, extruding, sand mold binding, foam andablative materials.

The polymeric resins of the invention are especially suitable for use inapplications wherein relatively high heat stabilities are required.Thus, these resins are useful in electric coils, for example; their usepermitting the use of higher voltages or the reduction of wirediameters. These resins are also useful in electric motors and inminiaturized electric devices and construction elements.

The polymeric resins of the invention are especially suitable for use inplastics reinforced with glass, quartz, carbon or aramide fibers, andthe like. With the increase in heat stability resulting from the use ofthe polymeric resins of the invention, these reinforced plastics can beused for applications not previously suited for plastics such as, forexample, in the replacement of metals or ceramic materials inheat-stressed construction applications. In these applications, the highbending resistance and impact strength of the resins of the inventionare particularly advantageous.

In order to illustrate the preparation of the 1-oxa-3-aza-tetralinegroup containing compounds that are useful in the preparation of thepolymeric resins of the invention, the following Examples 1-6 areprovided. In the following examples as well as throughout thespecification and claims, all parts and percentages are by weight andall temperatures are in degrees centigrade unless otherwise indicated.

EXAMPLE 1

.Iadd.To .Iaddend.210 grams of 30% formaldehyde (2.1 moles),.Iadd.contained in a stirred vessel equipped with reflux cooling andheated to a temperature of 80° C., .Iaddend.94 grams of phenol (1 mole)and 99 grams of 4,4'-diaminodiphenyl methane (0.5 mole) are added .[.toa stirred vessel equipped with reflux cooling and heated to atemperature of 80° C., for.]. .Iadd.within .Iaddend.15 minutes. Themixture is allowed to settle. The top aqueous layer is separated, andthe remaining water is distilled off in a vacuum at 100° C. Theresulting resin-like 1-oxa-3-aza tetraline group containing compound hasan N-equivalent weight of 217.

EXAMPLE 2

4.1 moles formaldehyde, 2 moles aniline, 1 mole of phenol and 0.5 molebisphenol A (2,2-bis(4-hydroxyphenyl)-propane) are reacted using theprocedures in Example 1. The resulting product has an N-equivalentweight of 221.

EXAMPLE 3

Formaldehyde, phenol and 1,4-diaminobenzol in mole ratio 2:1:0.5 arereacted using the procedures in Example 1. The resulting product has anN-equivalent weight of 172.

EXAMPLE 4

37.6 kilograms (400 moles) of phenol, 15 kilograms (200 moles) of 40%formaldehyde and 2 kilograms of 10% sulfuric acid are heated to 40° C.in a stirred vessel. The mixture exotherms to 96° C. The mixture ismaintained at 96° C. with stirring for 30 minutes. The mixture is cooledto room temperature and allowed to settle. The aqueous layer is removed.The remaining product is a phenol-Novolak mixture with an average numberof nuclei of 2, a water content of 15% and a phenol content of 22%. Theequivalent weight of phenol is 117.7.

EXAMPLE 5

157.5 grams (2.1 mole) of 40% formaldehyde containing 5 millimoles ofpotassium hydroxide, 117.7 grams of the product of Example 4 containing1 mole phenol hydroxyl groups, and 93 grams (1 mole) of aniline aremixed together for 7 minutes at 95° C. with stirring, then heated underreflux conditions for 30 minutes. The mixture is cooled to roomtemperature, allowed to settle and the aqueous layer is removed. Theresulting product is distilled under a vacuum and at a temperature of123° C. to remove remaining water. The product has an N-equivalentweight of 217.

EXAMPLE 6

A resin containing an average of 1.6 1-oxa-3-aza-tetraline groups permolecule is produced from 1.5 moles of formaldehyde, 1 gram equivalentof the product of Example 4, and 0.8 mole of aniline using theprocedures of Example 5. The resulting product has an N-equivalentweight of 240.5.

The following Examples 7-25 are provided to illustrate the preparationof the polymeric resins of the invention. In these examples, some of theepoxide resins identified in Table 1 are used. The remaining epoxideresins in Table 1 are also useful in making the polymeric resins of theinvention.

                  TABLE 1                                                         ______________________________________                                        Sym-                                                                          bol  Epoxide Resin                                                            ______________________________________                                        A    4-(1,2-epoxyethyl)-1,2-epoxycyclohexane                                  B    1,2,8,9-diepoxy-p-menthane                                               C    2,2-bis-(3,4-epoxycyclohexyl)-propane                                    D    Bis-(2,3-epoxycyclopentyl)ether(liquid form)                             E    Bis-(2,3-epoxycyclopentyl)ether(isomer crys-                                  talline form)                                                            F    1,2,5,6-diepoxy-4,7-hexahydromethanoindane                               G    1,1,1-tris((5-(1,2-epoxy)-4,7-hexahydromethano-                               indane oxy)methyl)-propane                                               H    1,2-bis(5(1,2-epoxy)4,7-hexahydromethanoindane                                oxy)-ethane                                                              I    3,4-epoxycyclohexane carboxylic acid-(3,4-                                    epoxycyclohexylmethyl)ester                                              K    3,4-epoxy-6-methylcyclohexane carboxylic acid-                                (3,4-epoxy-6-methylcyclohexylmethyl)ester                                L    2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)-                                 cyclohexane-m-dioxane                                                    M    2-(3,4-epoxy-4-methylcyclohexyl-5,5-spiro(3,4-                                epoxy)cyclohexane-m-dioxane                                              N    .[.2-(3,4-epoxy-4-methylcyclohexyl)-5,5-spiro(3,4-                            epoxy)-4-methyl cyclohexane-m-dioxane                                    O    2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)-4-                               methylcyclohexane-m-dioxane.].                                                .Iadd.2-(3,4-epoxy)cyclohexyl-5,5-                                            spiro(3,4-epoxy)-4-methylcyclohexane-                                         m-dioxane                                                                     2-(3,4-epoxy-4-methylcyclohexyl)-                                             5,5-spiro(3,4-epoxy)-4-methyl                                                 cyclohexane-m-dioxane.Iaddend.                                           P    2-(3,4-epoxy)-4,6-dimethylcyclohexyl-5,5-spiro-                               (3,4-epoxy)-4-methylcyclohexane-m-dioxane                                Q    2-(3,4-epoxy)-4,6-dimethylcyclohexyl-5,5-spiro-                               (3,4-epoxy)-4,6-dimethylcyclohexane-m-dioxane                            R    Bis-(3,4-epoxy-6-methylcyclohexylmethyl)adipate                          S    Bis-3,4-epoxycyclohexylmethyl)adipate                                    T    Bis(3,4-epoxy-cyclohexylmethyl)-terephthalate                            U    Bis-(3,4-epoxy-6-methylcyclohexylmethyl)-tere-                                phthalate                                                                V    4,5-epoxy-hexahydrophthalic acid-bis-(3,4-                                    epoxy-cyclohexylmethyl)ester                                                   ##STR9##                                                                G                                                                                   ##STR10##                                                               H                                                                                   ##STR11##                                                               L                                                                                   ##STR12##                                                               ______________________________________                                    

EXAMPLE 7

100 parts of the product of Example 1 are mixed at 140° C. with 100parts of epoxide resin I and poured under vacuum into a mold for a plate10 millimeters thick. The mixture is cured for one hour at 180° C., thenfor one hour at 200° C. and then for two hours at 220° C. Test bodiesprepared from the plate show no decomposition at 250° C. These bodieshave a bending resistance of 115 .[.MPs.]. .Iadd.MPas.Iaddend., an Emodulus of 4800 .[.MPs.]. .Iadd.MPas.Iaddend., an electrical resistanceover 10¹⁵ ohms and a loss factor of less than 10⁻². The glass transitiontemperature is 230° C. The term "glass transition" temperature is usedherein to refer to the temperature at which the polymer changes from abrittle, vitreous state to a plastic state.

EXAMPLES 8-23

Cast resin plates were prepared from the resin mixtures given in Table 2using the method described in Example 7. The epoxide resins used arelisted in Table 1. The properties of the cured resins are listed inTable 2.

                                      TABLE 2                                     __________________________________________________________________________    Example No.                                                                              8   9   10       11  12  13  14  15                                __________________________________________________________________________    1-Oxa-3-aza-tetra-                                                                        5   5   5        5   5   5   5   5                                line compound from                                                            Example No.                                                                   N--equavalent weight                                                                     217 217 217      217 217 217 217 217                               (1)                                                                           Wt. of 1-oxa-3-aza-                                                                      100 100 100      100 100 100 100 100                               tetraline compound, g                                                         Epoxide resin                                                                            K   S   L        L   L   L   L   L                                 Epoxide equivalent                                                                       140 (3)                                                                           183 (3)          162 (2)                                       weight                                                                        Wt. of epoxide, g                                                                        100 100 100       20  40  66  75 150                               Equivalent ratio (6)                                                                     1.55                                                                              1.18                                                                              1.36     0.27                                                                              0.54                                                                              0.9 1.0 2.0                               Curing cycle                                                                             (7) 180° C.→                                                            → →                                                                          →                                                                          →                                                                          →                                                                          →                                     (7) 200° C.→                                                            → →                                                                          →                                                                          →                                                                          →                                                                          →                                     (7) 220° C.→                                                            → →                                                                          →                                                                          →                                                                          →                                                                          →                          Recuring              (10) 250° C.                                     Behavior at                                                                         220° C.                                                                     (4) (4) (4)                                                                              (4)   (4) (4) (4) (4) (4)                                     250° C.                                                                     (4) (4) (4)                                                                              (4)   (4) (4) (4) (4) (5)                               Bending                                                                              25° C.                                                                         115    100-110                                                 resistance                                                                          220° C.  65                                                      at, MPs                                                                             250° C.  50                                                      Glass transition                                                                         .sup. 220°                                                                 .sup. 190°                                                                 250°                                                                      280°                                                                         .sup. 210°                                                                 .sup. 250°                                                                 >260°                                                                      >260°                                                                      >260°                      temperature, C.°                                                       __________________________________________________________________________    Example No.                                                                              16  17   18  19   20 21  22    23                                  __________________________________________________________________________    1-Oxa-3-aza-tetra-                                                                        5   5    2   3    6  5   5     5                                  line compound from                                                            Example No.                                                                   N-equavalent weight                                                                      217 217  231 172  240                                                                              217 217   217                                 (1)                                                                           Wt. of 1-oxa-3-aza-                                                                      100 100  100 100  100                                                                              100 100   100                                 tetraline compound, g                                                         Epoxide resin                                                                            I   O    R   I    L  R · L                                                                    K · A                                                                      A                                   Epoxide equivalent                                                                       126 (3)                                                                           147 (3)                                                                            197 (3)                                                                           160 (3)                                                                            -- --  70 (3)                                    weight                                                                        Wt. of epoxide, g                                                                        100 100  100 100   50                                                                              50 · 50                                                                  80 · 20                                                                     26                                 Equivalent ratio (6)                                                                     1.7 1.5  1.2 1.36 0.75                                                                             --  --    0.8                                 Curing cycle                                                                             →                                                                          →                                                                           →                                                                          →                                                                           →                                                                         →                                                                          (8) 140° C.                                                                  (8) 140° C.                             →                                                                          →                                                                           →                                                                          →                                                                           →                                                                         →                                                                          (9) 200° C.                                                                  (9) 160° C.                             →                                                                          →                                                                           →                                                                          →                                                                           →                                                                         →  (9) 200° C.                  Recuring                                                                      Behavior at                                                                         220° C.                                                                     (4) (4)  (4) (4)  (4)                                                                              (4) (4)   (4)                                       250° C.                                                                     (4) (4)  (4) (4)  (4)                                                                              (4) (4)   (5)                                 Bending                                                                              25° C.                                                                     115                                                                resistance                                                                          220° C.                                                          at, MPs                                                                             250° C.                                                          Glass transition                                                                         .sup. 230°                                                                 .sup. 220°                                                                  .sup. 200°                                                                 .sup. 240°                                                                  .sup. 180°                                                                .sup. 220°                                                                 .sup. 220°                                                                   .sup. 170°                   temperature, C.°                                                       __________________________________________________________________________     (1) Calculated from production.                                               (2) Analytically determined.                                                  (3) Calculated from theoretical formula.                                      (4) Unchanged                                                                 (5) Cracks and bubbles observed.                                              (6) Ratio of equivalents of 1oxa-3-aga-tetraline to epoxide.                  (7) 1 hour at                                                                 (8) 24 hours at                                                               (9) 2 hours at                                                                (10) 3 hours at                                                          

EXAMPLE 24

75 grams epoxide resin L are mixed, under vacuum at 120° C. with 100grams of the 1-oxa-3-aza-tetraline compound according to Example .Iadd.5.Iaddend.and 200 grams quartz meal, and poured into a mold. The castpiece is cured for 1 hour at 200° C., then for 1 hour at 220° C. Theresulting product has a bending resistance of 60 MPs and shows nodeformation at 250° C.

EXAMPLE 25

A glass cloth with a glycidyl-propyl silane finish and a .[.surfacearea.]. .Iadd.weight .Iaddend.of 120 grams per square meter isimpregnated with a 60% solution of the resin mixture of Example 21, anddried in a two-step hot air channel at 100°-140° C. Eight layers of thePrepreg are pressed between layers of copper foil for one hour at 180°C. to form a plate. The laminate shows no delamination in the solderbath test at 260° C. The electrical resistance is over 10¹⁵ ohm --cm,the loss factor under 0.01. The bending resistance amounts to 500 MPs.

EXAMPLES 26-28

Examples 26-28 are provided for purposes of comparison. Cast resinplates were prepared from resin mixtures provided in Table 3. InExamples 26 and 27, cycloaliphatic epoxide resins other than the typerequired by the present invention were used. In Example 28, themonofunctional 1-oxa-3-aza-tetraline compound disclosed in Example 1 ofSwiss Pat. No. 579,113 was used. The results of these examples indicatethat polymers with less heat stability or lower glass transitiontempertures were achieved when compared to the polymeric resins of theinvention.

                                      TABLE 3                                     __________________________________________________________________________    Example No.  26        27        28                                           __________________________________________________________________________    1-Oxa-3-aza-tetraline                                                                       5         5        N--Phenyl-1-oxa-3-ara-                       compound from Example            tetraline                                    No.                                                                           N--equivalent (1)                                                             Wt. of 1-oxa-3-aza-                                                                        100       100       100                                          tetraline compound, g.                                                        Epoxide resin                                                                              Tetrahydrophthalic                                                                      Hexahydrophthalic                                                                        1                                                        acid diglycidylester                                                                    acid diglycidylester                                   Epoxide equivalent               140 (1)                                      Wt. of epoxide, g.                                                                         100       100        40                                          Equivalent ratio (6)             0.60                                         Curing cycle 2 hrs. at 180° C.                                                                2 hrs. at 180° C.                                                                2 hrs. at 160° C.                                  .sup. 1 hr. at 200° C.                                                           .sup. 1 hr. at 200° C.                                                           .sup. 1 hr. at 200° C.                Behavior at 220° C.                                                                 (5)       (5)       (4)                                          Glass transition temp-           110° C.                               erature, °C.                                                           __________________________________________________________________________     (1) Calculated from production.                                               (2) Analytically determined.                                                  (3) Calculated from theoretical formula.                                      (4) Unchanged                                                                 (5) Cracks and bubbles observed.                                              (6) Ratio of equivalents of 1oxa-3-aza-tetraline to epoxide.             

The polymeric resins of the invention obtained in the above examplesshow, in comparison with the structurally closest previously knownresins, of which the properties are well known, a generally far higherheat resistance, along with very good mechanical properties, especiallywith high bending and impact resistance. The comparison tests (Examples26-28) confirm this observation.

While the invention has been explained in relation to its preferredembodiments, it is to be understood that various modifications thereofwill become apparent to those skilled in the art upon reading thisspecification. Therefore, it is to be understood that the inventiondisclosed herein is intended to cover such modifications as fall withinthe scope of the appended claims.

I claim:
 1. A composition comprising a polymeric resin derived from(A)at least one compound containing an average of more than one1-oxa-3-aza-tetraline group per molecule .[.with.]. .Iadd.and/or theprepolymers thereof with .Iaddend. (B) at least one cycloaliphaticepoxide containing at least two epoxide groups, at least one of saidepoxide groups being part of said ring, the .[.mole.]. ratio of .[.(B)to (A).]. .Iadd.epoxide groups to 1-oxa-3-aza-tetraline groups.Iaddend.being in the range of about 0.2 to about
 2. 2. The compositionof claim 1 wherein component (B) has at least one epoxide group directlyattached to said ring.
 3. The composition according to claim 1, whereinsaid 1-oxa-3-aza-tetraline groups include an aromatic substituent at thenitrogen atom.
 4. The composition of claim 1 wherein component (A) isthe reaction product of at least one amine, at least one phenol, andformaldehyde.
 5. The composition of claim 4 wherein said phenol isselected from the group consisting of phenol, m- and p-cresol, m- andp-ethyl-phenol, m- and p-isopropylphenol, m- and p-methoxy-phenol, m-and p-ethoxyphenol, m- and p-isopropyloxy-phenol, m- and p-chlorophenoland B-naphthol.
 6. The composition of claim 4 wherein said phenol isselected from the group consisting of 4,4'-dihydroxydiphenylmethane,3,3'-dihydroxy-diphenylmethane, 2,2-bis-(4-hydroxy-phenyl)-propane,4,4'-dihydroxystilbene, hydroquinone, pyrocatechin and resorcin.
 7. Thecomposition of claim 4 wherein said amine is selected from the groupconsisting of aniline, o-, m- and p-phenylene diamine, benzidine,4,4'-diaminodiphenyl methane, and 2,2-bis-(aminophenyl)propane.
 8. Thecomposition of claim 1 wherein component (A) is .Iadd.derived from.Iaddend.a Novolak resin.
 9. The composition of claim 1 whereincomponent (B) has an equivalent weight in the range of about 70 to about250.
 10. The composition of claim 1 wherein component (B) has anequivalent weight in the range of about 120 to about
 200. 11. Thecomposition of claim 1 wherein component (B) is selected from the groupconsisting of2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, 1 to4 times methylated2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane,4-(1,2-epoxyethyl)-1,2-epoxycyclohexane, .[.1,2,8,9-diepoxy-p-methane,2,2-bis(3,4-epoxycyclohexyl)propane.].,.Iadd.1,2,8,9-diepoxy-p-menthane, 2,2-bis(3,4-epoxycyclohexyl)propane.Iaddend.bis-(2,3-epoxycyclopentyl)ether,1,2,5,6-diepoxy-4,7-hexahydromethanoindane,bis-(3,4-epoxy-cyclohexylmethyl)adipate,bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate,bis(3,4-epoxy-cyclohexylmethyl)terephthalate,bis(3,4-epoxy-6-methyl-cyclohexylmethyl)-terephthalate,3,4-epoxy-cyclohexanecarboxylic acid-(3,4-epoxy-cyclohexylmethyl)ester,3,4-epoxy-6-methylcyclohexanecarboxylicacid-(3,4-epoxy-6-methylcyclohexylmethyl)ester,1,2-bis-(5(1,2-epoxy)-4,7-hexahydromethanoindaneoxy)-ethane,.[.1,1,1-tris((5-(1,2-epoxy)-4,7-hexahydromethynoindaneoxy)-methyl)-propane.]..Iadd.1,1,1-tris((5-(1,2-epoxy)-4,7-hexahydromethanoindaneoxy)-methyl)propane.Iaddend.and 4,5-epoxyhexahydrophthalicacid-bis-(3,4-epoxycyclohexylmethyl)ester.
 12. The composition of claim1 wherein component (B) is selected from the group consisting of2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, 1 to4 times methylated2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane,bis(3,4-epoxy-cyclohexylmethyl)adipate,bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate,3,4-epoxy-cyclohexane-carboxylic acid-(3,4-epoxy-cyclohexylmethyl)esterand 3,4-epoxy-6-methylcyclohexane carboxylicacid-(3,4-epoxy-6-methylcyclohexylmethyl)ester.
 13. The composition ofclaim 1 wherein component (B) is represented by the formula

    X--Y

wherein: X is a 3,4-epoxycyclohexyl group or a mono- or dimethylsubstituted 3,4-epoxycyclohexyl group; and Y is a group represented bythe formula ##STR13## wherein n is a number in the range of from zero to2, or a group represented by the formula ##STR14## or a grouprepresented by the formulae

    --COO--CH.sub.2 --X

or

    --CH.sub.2 --Z--CH.sub.2 --X

wherein: X is as defined above, and Z is .[.derived from.]. .Iadd.theacid radical of .Iaddend.an aliphatic, cycloaliphatic or aromaticdicarboxylic acid group.
 14. The composition of claim 1 wherein.[.the.]. .Iadd.said .Iaddend.mole ratio .[.of (B) to (A).]. is in therange of from about 0.8 to about 1.5.
 15. The composition of claim 1wherein components (A) and (B) are reacted at a temperature in the rangeof about 50° C. to about 300° C.
 16. The composition of claim 1 whereincomponents (A) and (B) are reacted at a temperature in the range ofabout 100° C. to about 250° C.
 17. The composition of claim 1 whereincomponents (A) and (B) are reacted at a temperature in the range ofabout 140° C. to about 230° C.
 18. The composition of claim 1 whereincomponents (A) and (B) are reacted in the presence of an effectiveamount of catalyst to accelerate the reaction.